DE4006191A1 - Compsns. for removing water from surfaces - Google Patents

Abstract

Compsns. (I) contg. 99.99-90 wt% dichloro-pentafluoro-propane (II) or a mixt. of (II) and 0.01-10 wt% surfactant(s) (III) dissolved in (II). Amts. are 99.95-95 wt% (II) and 0.05-5 wt% (III); (II) is 1,1-dichloro-2,2,3,3,3- pentafluoropropane (R225ca) or 1,3-dichloro-1,1,2,2,3 -pentafluoropropane (R225cb); (III) are surface-active organic amines, ammonium cpds. or amides, organic acids or phosphate esters, or salts of amines, etc. with organic acids or mono- or di-esters of phosphoric acid, pref. a mixt. of an amine and an organic acid or phosphate ester in the mol. ratio (0.3:0.7)-(0.55-0.45); amine is a linear or branched 8-12C alkylamine, pref. nonyl-, octyl- or 2-ethylhexyl-amine; organic acid is a 8-12C carboxylic acid, pref. octanoic acid, and phosphate ester is an alkyl, aryl or aryl-alkyl phosphate, pref. tri(2-ethylhexyl), tri(n-butyl), triphenyl or diphenyl-(2-ethylhexyl) phosphate.

Description

The present invention relates to compositions based on the chlorofluorocarbons containing hydrogen from the group of dichloropentafluoropropane and the use of these compositions for Removal of water from surfaces of objects of all kinds and from all kinds of materials.

With many machining and cleaning processes, e.g. B. in the electrical or electronics industry optical industry, as well as z. B. in mechanical Industry in the manufacture of high quality precision workpieces objects come with water or moisture wanted or even unwanted touch. These items can therefore adhere water (e.g. as a moisture film). In the presence of adhering water it can become but in terms of further processing steps that Functionality and the lifespan of the objects adversely affect. It is therefore necessary that many Items immediately after editing or Cleaning operations involving the presence of water or even after mere contact with air humidity etc. before further processing or for the functional Completely free of sticking water will.  

The removal of water from the objects will hereinafter also referred to as drying or drying. In the prior art, objects are dried for drying the objects, depending on their type, by heating or by treatment with compositions ("drying compositions") from certain solvents (such as Hydrocarbons, acetone, alcohols, or fully halogenated Chlorofluorocarbons) and surface-active Dried substances. Because the items to be dried made of different materials, e.g. B. from Plastics, glass, metals or combinations thereof the drying process and the drying compositions used for drying with a variety of materials. Drying heating generally represents an undesirable very high thermal load for the items to be dried Items or comes because of the high applicable Temperatures for a wide range of materials out of the question. Also in many cases this way area-free drying is not possible. The parts in the drying compositions, in particular the solvent forming the main component, should stand out against a multitude of different ones Keep materials inert.

Many efforts have already been made around for different areas of application and for different Materials drying compositions with the desired Properties such as B. high drying effect, drying quality or good inertness towards the ones to be dried Objects to achieve, but are the well-known Compositions in their application technology, toxicological and environmental properties still in need of improvement. The high demands with regard to inertness, drying effect and drying quality are known by the known compositions of State of the art not always or often only unsatisfactorily  Fulfills. Or other known compositions contain larger proportions of toxicologically and under Security aspects (low flash point) concern Solvents. Other compositions contain solvent components, for the environment because of it influencing properties a replacement by others, for the respective purposes at least equally well-suited solvent is desirable. It exists hence a need for new drying compositions with improved properties that also go beyond regarding the criteria toxicology and in particular Environmental impact have increased safety.

The task was therefore to create new compositions for water removal (drying) from surfaces of To provide items that have the disadvantages overcome the state of the art and for water removal are particularly well suited.

To achieve this object, the invention proposes new ones Compositions that are characterized by a content of 99.99 to 90% by weight of a dichloropentafluoropropane or a mixture of dichloropentafluoropropanes and 0.01 up to 10% by weight of a surfactant dissolved therein Substance or a mixture of these surfactants Mark out substances, the sum of the components Is 100% by weight.

In an expedient sub-variant of the invention the compositions are characterized in that they 99.95 to 95 wt .-% of dichloropentafluoropropane and Contain 0.05 to 5% by weight of the surface-active substance, the sum of the components being 100% by weight.

Dichloropentafluoropropanes are in the sense of the invention the chlorofluorocarbons carrying a hydrogen atom the empirical formula C₃HCl₂F₅. It is in particular  the non-fully halogenated isomeric chlorofluorocarbons 1,2-dichloro-1,1,2,3,3-pentafluoropropane, 2,3-dichloro-1,1,1,2,3-pentafluoropropane, 1,1-dichloro- 2,2,3,3,3-pentafluoropropane (= 3,3-dichloro-1,1,1,2,2- pentafluoropropane), 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane, 1,2-dichloro- 1,1,3,3,3-pentafluoropropane, 1,1-dichloro-1,2,3,3,3-pentafluoropropane. Preferred dichloropentafluoropropanes are 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R225ca) and 1,3- Dichloro-1,1,2,2,3-pentafluoropropane (R225cb).

The drying compositions of the invention can contain any surfactant per se, which Solvent-soluble (i.e. here soluble in dichloropentafluoropropane) and which is the repression or removal of water from the surfaces of the to be dried Objects made easier by the dichloropentafluoropropane. Such surface-active substances are useful Refinements of the compositions according to the invention selected from the groups of surface-active organic Amine, ammonium and amide compounds, the surface-active organic acids, the surface-active Phosphoric acid ester, the salts from a) surface-active organic amine, ammonium or amide compounds with b) surface-active organic acids, phosphoric acid mono- or phosphoric acid diesters, and mixtures thereof.

The surface-active organic amine compounds in the sense of the invention can be derived from mono- and diamine compounds. In the subgroup of monoamine compounds, these can be primary, secondary or tertiary amines, for example mono-, di- and trialkylamines, the alkyl radicals of which can be straight-chain or branched, saturated or unsaturated, partially halogenated or perfluorinated and whose alkyl radicals can also be other functional groups, such as, for example, . B. hydroxy groups can wear. The amine compounds can e.g. B. may also be amines which are partly substituted with oxyalkylene groups in addition to alkyl radicals. Examples of monoamine compounds are C8 to C12 alkylamines, such as in particular nonylamine, octylamine or 2-ethylhexylamine; Fluoramines of the general formula R _F -X-NR¹R², in which R _{F is} a perfluorinated alkyl radical having up to 20 C atoms, X is a saturated or unsaturated, optionally partially halogenated C1 to C5 alkylene radical and R¹ and / or R² is hydrogen, lower alkyl radicals (ie C1 to C4 alkyl radicals) or hydroxy group-substituted lower alkyl radicals, such as in particular, for. Fluorine amines such as R _F C₂H₄NH₂, R _F C₂H₄N (C₂H₅) ₂, R _F CF = CH-CH₂N (C₂H₅) ₂, R _F C₂H₄NHC₂H₄OH, R _F CF = CH-CH₂NHC₂H₄OH, R _F C₂H₄N (C₂H₄OH) ₂ and R _F CF = CHCH₂N (C₂H₄OH) ₂; Oxyalkyl-substituted amines of the general formula

wherein R³ is a C6 to C20 alkyl radical, R⁴ and / or R⁵ is hydrogen or methyl and k and / or l for are an integer from 1 to 5.

The monoamine compounds are derived, for example also surface active ammonium compounds in Sense of the invention. On the one hand, these can be salts of primary, secondary and tertiary described above Amines with inorganic acids. On the other hand the amine compounds can also be quaternary ammonium salts be, whose N atom is substituted by four organic radicals is. Such quaternary ammonium compounds are sufficient e.g. B. the general formula R₂N⁺R'₂, wherein R is a C6 to C8-alkyl radical and R 'are a C1- to C2-alkyl radical. Other quaternary ammonium compounds are other than alkyl also partially substituted with oxyalkyl groups and suffice z. B. the general formula

wherein R³ is a C6 to C20 alkyl radical, R⁶ one C1- to C10-alkyl radical, R⁴ and / or R⁵ is hydrogen or methyl and k and / or l for an integer from 1 to 5.

In the subgroup of the diamine compounds of the surface-active organic amine compounds in the sense of the invention, the two amino groups contained in these compounds are linked by an alkylene chain with up to 20 C atoms. The two amino groups of the diamine compound can each be primary, secondary or tertiary amino groups. Such diamine compounds are sufficient for. B. the general formula R⁷R⁸N-Y-NR⁹R¹⁰, wherein Y is a C4- to C20-alkylene chain and R⁷, R⁸, R⁹ and / or R¹⁰ for hydrogen, for C1- to C6-alkyl radicals or for ethoxy-substituted C1- to C6 -Alkyl residues stand; Examples of these diamine compounds are in particular 1,4-butanediamine, 1,6-hexanediamine and 1,12-dodecanediamine. Other diamine compounds are sufficient for. B. the general formula R¹¹-NH- (CH₂) _m -NH₂, where m is an integer from 1 to 9 and R¹¹ is an aliphatic, optionally unsaturated, C1- to C25-alkyl radical; Examples of such diamine compounds are, in particular, oleylamino-propylene amine, stearylamino-propylene amine, palmity aminopropylene amine.

Surface-active monoamide compounds in the sense of the invention are also derived from the diamine compounds, for example. Such monoamide compounds are sufficient for. B. the general formula R _F (CH₂) _n -Z-NH- (CH₂) ₀-NR¹²R¹³, wherein R _{F is} a perfluorinated alkyl radical having up to 20 C atoms, Z is sulfonyl or carbonyl, R¹² and / or R¹³ lower alkyl radicals (ie C1 to C4 alkyl radicals) and n and / or o represent an integer from 1 to 5. Examples of such surface-active monoamide compounds are in particular, for. B. the compounds R _F C₂H₄SO₂NHCH₂CH₂CH₂N (CH₃) ₂, R _F C₂H₄CONHCH₂CH₂CH₂N (CH₃) ₂, R _F CO₂NHCH₂CH₂CH₂N (CH₃) ₂ and R _F CONHCH₂CH₂CH₂N (CH₃) ₂.

To the surface-active substances from the group The amide compounds also include diamide compounds that e.g. B. the general formula

suffice in which R¹¹ is an aliphatic, optionally means unsaturated C1 to C25 alkyl radical, R¹⁴ one aliphatic C10 to C30 alkyl radical with a double bond means and p is an integer from 1 to 9 stands. Examples of such diamide compounds are Dioleyl oleylamido propylene amide, diundecylenyl oleyl amido propylene amide, Dioleyl-stearylamido-propylene amide, dioleyl palmitylamido-propylenamide and dilinoleyl-oleylamido propylene amide.

The surface-active organic acids in the sense of the invention include dicarboxylic acids HOOC- (CH₂) _q -COOH with q equal to an integer from 1 to 10; Monocarboxylic acids R¹⁵-COOH, organic sulfonic acids R¹⁵-SO₃H and monoesters of sulfuric acid R¹⁵-OSO₃H; the radical R¹⁵ has the meaning of a saturated or unsaturated, optionally hydroxyl-substituted, C1- to C20-alkyl radical or a C7- to C26-alkylphenyl radical in the organic acids mentioned. Examples of such surface-active organic acids are e.g. B. malonic acid, succinic acid, succinic acid, dodecanedioic acid etc .: C8- to C12-carboxylic acids such as in particular octanoic acid, nonanoic acid; Fatty acids such as oleic acid, stearic acid, palmitic acid; Alkyl sulfonic acids such as alkyl benzene sulfonates.

For the purposes of the invention, the surface-active phosphoric acid esters include phosphoric acid mono-, phosphoric acid di- and phosphoric acid triesters, ie there are phosphoric acid compounds in which one, two or all three hydroxyl groups of phosphoric acid have the same or different, unbranched or branched, saturated or unsaturated alkyl groups Aryl groups are esterified by alkyl-substituted aryl groups or also by oxyalkylene groups or optionally oxyalkylene groups modified by monocyclic aromatic groups. Such phosphoric acid esters are sufficient, for. B. the general formula (R¹⁶O) (R¹⁷O) (R¹⁸O) P = O. The radical R¹⁶ here is a straight-chain or branched C1 to C20 alkyl radical, a C7 to C26 alkylphenyl radical, a phenyl radical, a C6 to C26 ethoxyalkyl radical, and also an oxyalkylene radical or an oxyalkylene radical modified by a monocyclic aromatic group of the formula -T- (OC _r H _2r ) ₅-OH; T here stands for a saturated or unsaturated alkylene radical, for an arylene radical or for a divalent aliphatic-aromatic radical, where the radical T can have up to 40 C atoms, and s is an integer between 2 and 30 and r is 2, 3 or 4. The radicals R¹⁷ and R¹⁸ both represent hydrogen in the case of phosphoric acid monoesters and the radicals R¹⁷ and R¹⁸ independently of one another have the meaning of R¹⁶ in the case of phosphoric acid triesters. In the case of phosphoric acid diesters, one of the radicals R¹⁷ and R¹⁸ is hydrogen and the remaining radicals is R¹⁶. Examples of surface-active substances from the group of phosphoric acid esters are in particular, for. B. butyl phosphate, octyl phosphate, decyl phosphate, 2-ethylhexyl phosphate, didecyl phosphate, didodecyl phosphate, di- (3,6-dioxapentadecyl) phosphate, tri- (2-ethylhexyl) phosphate, tri-n-butyl phosphate, triphenyl phosphate or diphenyl (2 -ethylhexyl) phosphate.

Another group of surface-active substances in the sense of the invention are salts of a) surface-active organic amine, ammonium or amide compounds with b) surface-active organic acids, phosphoric acid mono- or phosphoric acid diesters. These salts can be, for example, combinations of the diamines of the formula R⁷R⁸N-Y-NR⁹R¹⁰ described above and the above-described phosphoric acid mono- or phosphoric acid diesters of the formula (R¹⁶O) (R¹⁷O) (R¹⁸O) P = O with R¹⁷ being hydrogen. Examples of such salts are in particular 1,12-dodecanediammonium bis (decylphosphate), 1,12-dodecanediammonium bis (didodecylphosphate), 1,6-hexanediammonium bis (2-ethylhexylphosphate), 1,12- Dodecanediammonium bis (di-3,6-dioxapentadecyl phosphate), 1,4-butanediammonium bis (di-3,6-dioxapentadecyl phosphate), 1-aminododecyl-12-ammonium didecyl phosphate, 1-aminododecyl-12- ammonium didodecyl phosphate, 1-aminododecyl 12 ammonium (di-3,6-didoxapentadecyl phosphate) and 1-aminohexyl 6ammonium didodecyl phosphate. Furthermore, the salts can also be combinations of aliphatic C10 to C20 carboxylic acids with a double bond and on the one hand the above-described diamines of the formula R¹¹-NH- (CH₂) _m -NH₂ or on the other hand the above-described diamides of the formula

be. On the one hand, examples of these salts are in particular e.g. B. oleylaminopropylene amine dioleate, oleyl aminopropylene amine diundecylenate, stearylaminopropyleneamine dioleate, Palmitylaminopropylenamin-dioleate and Oleylaminopropylenamin- dilinoleate or on the other hand especially z. B. Dioleyl oleylamidopropylene amide, diundecylenyl oleylamidopropylene amide, Dioleyl-stearylamidopropylene amide, dioleyl palmitylamidopropylene amide and dilinoleyl oleyl amidopropylene amide. Other salts in this group of surfactants Substances in the sense of the invention are sufficient for. B. the general formula

wherein R¹¹ is a saturated or unsaturated aliphatic C1 to C25 radical means R¹⁹ a C10 to C30 alkyl radical with at least one double bond and additional Substitution by a hydroxyl group or an acrylic residue means and m represents an integer from 1 to 9. Another group of salts is sufficient e.g. B. the general formula

wherein R¹⁵ has the meaning of a saturated or unsaturated, optionally hydroxyl-substituted, C1- to C20-alkyl radical or a C7 to C26-alkylphenyl radical owns and R²⁰, R²¹ and / or R²² for hydrogen or for an optionally substituted with hydroxyl groups, C1 to C20 alkyl radical.

In an expedient embodiment of the invention there are compositions that are considered surface-active Substances a mixture of a) a surface-active organic amine compound with b) a surface-active organic acid or with a surfactant Phosphoric acid esters in a molar ratio of a: b of 0.3: 0.7 to 0.55: 0.45 included.

In particularly advantageous embodiments of the invention contain the compositions as surfactants organic amine compound a straight-chain or branched C8 to C12 alkylamine. Amines are particularly preferred Nonylamine, octylamine or 2-ethylhexylamine.  

In another advantageous embodiment of the invention Compositions contain these as surfactant is an organic acid which is a C8 to C12 carboxylic acid, preferably octanoic acid.

In a further advantageous embodiment of the invention Compositions contain these as surface active substances phosphoric acid esters Are alkyl, aryl or aryl alkyl phosphates. Particularly preferred Phosphoric acid esters are e.g. B. Tri- (2-ethylhexyl) - phosphate, tri-n-butyl phosphate, triphenyl phosphate or Diphenyl (2-ethylhexyl) phosphate.

The compositions of the invention described above are liquid homogeneous compositions with an unusual effectiveness for removal of water from surfaces of objects. Another The invention therefore relates to water removal of surfaces of objects using the compositions according to the invention.

Furthermore, the invention also relates to a method for Water removal from surfaces of objects, which is characterized in that the surfaces with the Compositions according to the invention described above treated.

Compositions are available through the invention made particularly good for the removal of Suitable for water from surfaces of solid objects are. The surfaces to be treated, the damp, wet with water and / or coated with liquid water, can very well by the treatment with the invention Free compositions from adhering water, d. H. dried. Contacting the surfaces with the compositions according to the invention can be sprayed on, Brushing or something else Application of the composition by directing the  Composition over the surfaces or by immersion the objects happen in the composition. When using of immersion techniques, the composition moved or stirred in a suitable manner or in another Way in their effect, e.g. B. by ultrasound, get supported.

The removal of the water can take place at temperatures of above the solidification point from water to the boiling point the composition and / or the temperature at which water is still in a liquid state will. The time of treatment is not special critical as a significant amount of water from the Surfaces after the initial contact of the surfaces removed with the compositions according to the invention becomes. For practical purposes, it is usually recommended that the surfaces to be dried with the composition should be in contact for about 1 minute, although - depending on the respective surfaces of the material to be dried or the respective circumstances of the drying process - applied longer or shorter times can be. If desired, the solid object after drying with fresh, liquid and / or vapor Chlorofluorocarbon (preferably a Dichloropentafluoropropane) and / or another non-aqueous, solvents relatively inert to the surfaces be rinsed to remove any remaining to remove surface-active substances. Finally, if desired, the objects the drying adhering liquid chlorofluorocarbon from the surfaces by conventional techniques, for example by evaporation.

The compositions according to the invention meet all criteria for a good composition for the Removal of water from surfaces apply. So enable effective drying of objects different materials. They are equally suitable  good for objects made of metal, glass, fireproof Materials, from precious stones or from usual Plastics. This is how water is removed quickly and as completely as possible. The compositions do not form emulsions with water and allow rapid formation of a separate water and solvent phase. This criterion is very important because in the case of emulsion formation, water on the one hand accumulate in the compositions and on the other hand Part of the composition with the water to be discharged the drying stage could be removed and thereby the phase separation of water and solvent difficult would. Finally, the compositions of the invention stable over a long period of use, d. H. they do not become impoverished or only to a minor extent on the surface-active substances contained in dichloropentafluoropropane Substances. The surface-active substances are hardly or not at all due to the water to be discharged extracted from the dichloropentafluoropropanes because the Affinity of the dichloropentafluoropropanes in particular to the preferably used surfactants larger is as the affinity of water for these surfactants Substances. Furthermore, the invention Compositions no flash points.

The invention is intended to be illustrated below by means of examples are further explained, but without their scope to restrict.

Examples

In a commercially available 3-chamber drying system were drying experiments with objects from different Materials made. The 3-chamber Drying system consisted of one drying bath and two arranged in cascade to the drying bath Rinsing belts, the second rinsing bath with an overflow to the first rinsing bath and the first rinsing bath with one  Overflow to the drying bath was provided over the three Baths spanned a common steam room that followed above for the purpose of solvent condensation with a Cooling zone was provided. The separated in the cooling zone and collected condensate was through a return line recirculated to the second rinse bath. All three chambers the drying plant were additionally with separate heating devices fitted. The drying bath was through an overflow connected to a water separation device, in which the drying composition from the water was separated by separation. From the water separator was the drying composition after the Water separation by means of a pump via a return line recirculated into the drying bath.

The items were initially dried 1 minute in the drying bath with boiling drying composition submerged. After drying in the drying bath became the object to be dried in the two rinsing baths each with boiling dichloropentafluoropropane for rinsed for 1 minute each with immersion. After 1 minute The one to be dried stayed in the vapor phase Object the system absolutely dry and cool enough to be touched.

The drying bath and rinsing bath compositions that Drying conditions, the type of items to be dried and the drying results are in Table 1 reproduced. The designation R225ca stands for 1,1-dichloro-2,2,3,3,3-pentafluoropropane.  

Table 1

Claims (10)

1. Compositions characterized by a content of 99.99 to 90% by weight of a dichloropentafluoropropane or a mixture of dichloropentafluoropropanes and 0.01 to 10% by weight of a surface-active substance dissolved therein or a mixture of these surface-active substances, the Sum of the components is 100% by weight. 2. Compositions according to claim 1, characterized by a content of 99.95 to 95 wt .-% of dichloropentafluoropropane and 0.05 to 5% by weight of the surfactants Substance, the sum of its components Is 100% by weight. 3. Compositions according to one of the preceding Claims, characterized in that the dichloropentafluoropropane 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R225ca) or 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R225cb) is. 4. Compositions according to one of the preceding Claims, characterized in that the surface-active Substance is selected from the groups of surfactants organic amine, ammonium and amide compounds, the surface-active organic acids, the surface-active phosphoric acid ester, the salts a) surface-active organic amine, ammonium or Amide compounds with b) surface-active organic Acids, phosphoric acid mono- or phosphoric acid diesters, as well as mixtures thereof.   5. Compositions according to one of the preceding Claims, characterized in that they are surface-active Substances a mixture of a) an organic Amine compound with b) an organic acid or with a phosphoric acid ester in a molar ratio of a: b from 0.3: 0.7 to 0.55: 0.45 included. 6. Compositions according to one of claims 4 and 5, characterized in that the organic amine compound a straight-chain or branched C8 to C12 alkylamine, preferably nonylamine, octylamine or 2-ethylhexylamine, is. 7. Compositions according to one of claims 4 and 5, characterized in that the organic acid C8 to C12 carboxylic acid, preferably octanoic acid. 8. Compositions according to one of claims 4 and 5, characterized in that the phosphoric acid ester Alkyl, aryl or aryl alkyl phosphates, preferably Tri (2-ethylhexyl) phosphate, tri-n-butyl phosphate, triphenyl phosphate or diphenyl (2-ethylhexyl) phosphate, are. 9. Use of the compositions according to one of the Claims 1 to 8 for water removal from surfaces of Objects. 10. Process for water removal from surfaces of Objects, characterized in that the surfaces with compositions according to one of claims 1 treated to 8.